WO1998017712A1

WO1998017712A1 - Fluorinated resin films and pressure-sensitive adhesive sheets

Info

Publication number: WO1998017712A1
Application number: PCT/JP1997/003801
Authority: WO
Inventors: Nobuhiko Tsuda; Ryuji Iwakiri; Katsuhiko Imoto; Masaru Nagato
Original assignee: Daikin Industries, Ltd.
Priority date: 1996-10-22
Filing date: 1997-10-22
Publication date: 1998-04-30
Also published as: EP0945480A1; CN1234045A; CN1095856C; EP0945480A4; JPH10120801A; KR20000049189A; TW412555B

Abstract

Synthetic resin films which can be produced without using any organic solvent, are excellent in weathering and stain resistances, have processability enabling the formation of thinner films, and permit surface printing; and pressure-sensitive adhesive sheets made by using the same. Specifically, a fluorinated resin film produced by casting and having a modulus of elasticity of 50 kg/mm2 or above and an elongation of 50 % or above; and another fluorinated resin film produced by spreading an aqueous dispersion of a solvent-insoluble fluorinated resin on a non-adhesive substrate and drying the spread dispersion.

Description

I Description Fluorinated resin film and adhesive sheet Technical field

The present invention relates to a fluorine-containing resin film having excellent weather resistance and stain removal properties. Background art

Synthetic resins such as vinyl chloride resin, polyester resin, and vinyl acetate resin are widely used in a wide range of fields such as residential building materials, outdoor buildings, signboards, sign boards, and traffic signs due to their excellent workability. . Above all, those obtained by processing these synthetic resins into films and further applying an adhesive to form adhesive sheets are widely used as surface protective films or marking films.

Such a synthetic resin film is used as a signboard that emphasizes the image of a product when it is used outdoors and if the synthetic resin that composes it has poor weather resistance, it may discolor or fade due to aging. There have been problems such as a decrease in function, a deterioration in the aesthetic appearance of the interior of a house, and a decrease in the function as a traffic sign whose color is significant, which may cause a traffic accident. Further, depending on the type of these synthetic resins, there is a problem that the surface is easily contaminated due to bleeding of the plasticizer contained in the synthetic resins.

Therefore, a film made of a fluorine-containing resin has been proposed for the purpose of improving weather resistance. However, since a fluorine-containing resin generally has high crystallinity and has a high melting point or a high molecular weight, it is difficult for the resin to melt and flow. At present, to form a fluororesin film, extrusion molding is performed at a high temperature, or casting from a disposable organic solvent is performed.

Regardless of the fluororesin film obtained by such a method, it is difficult to efficiently produce a thin film having a thickness of several + m or less.

In order to solve such problems, Japanese Patent Publication No. Hei 7-62079 discloses a method of forming a film by casting a solvent from an organic solvent solution of a solvent-soluble synthetic resin. Proposed. However, in this method, the synthetic resin is limited to a solvent-soluble one, and the resulting film does not sufficiently satisfy the performance required for a marking film or the like that is hard and has elongation.

In addition, in this method, it is essential to use an organic solvent that is harmful to the human body, so there were also problems in the working environment such as the cost for removing and collecting the solvent and the safety.

Furthermore, a film molded from a fluorine-containing resin may be imparted with decorative properties by printing such as conventionally known offset printing, gravure printing, etc. due to the non-adhesive and non-adhesive properties of fluorine. It was so difficult that it had the disadvantage of poor versatility. Summary of the Invention

In view of the above situation, the present invention does not use an organic solvent in the production stage, has excellent weather resistance and contamination removal properties, has workability capable of forming a thin film, and is capable of surface printing. It is an object of the present invention to provide a certain synthetic resin film and an adhesive sheet using the same.

The fluorinated resin film of the present invention is a fluorinated resin film produced by a casting method, and has an elastic modulus of 50 kg / mm ² or more and an elongation of 50% or more. Detailed Disclosure of the Invention

The above-mentioned casting method refers to a method of dissolving or dispersing in a liquid medium such as water or an organic solvent, spreading the solution on a substrate, and evaporating the liquid medium at room temperature or in a heated state to obtain a film. A method in which a solution in which a resin is dissolved in an organic solvent is spread on a base material, and then the organic solvent is volatilized; a method in which an aqueous dispersion of the resin is spread on the base material, and then the aqueous medium is volatilized. And the like.

The above elastic modulus and elongation are measured at around room temperature and at 25 ° C in accordance with JISK6301. In the above measurement, if the organic solvent used at the time of casting remains in the film, the solution may show a high elongation due to the plastic effect immediately after the film is prepared, even if it shows high elongation. Since the plasticizing effect is lost due to volatilization of the agent and the like, the film does not elongate and cracks and cracks occur during use. Therefore, the measurement is performed with no organic solvent or the like contained in the film.

If the above elastic modulus is less than 50 kg Zm ni ² , the contamination resistance and the stain removal property of the film decrease due to the infiltration of contaminants. If the elongation is less than 50%, cracking, whitening, etc. of the film will occur during film processing and after adhesion sheet processing and adhesion to a curved surface. Preferably, the elongation is at least 80%.

The fluorine-containing resin film of the present invention can be obtained by spreading a fluorine-containing resin aqueous dispersion obtained by dispersing a resin in an aqueous medium on a non-adhesive substrate and drying. The solid concentration of the aqueous fluororesin dispersion is generally about 20 to 60% by weight, and the average particle size of the particles is about 50 to 300 nm. The pH of the aqueous dispersion is usually 5 to 10.

The fluororesin film of the present invention is obtained by extending the above fluororesin aqueous dispersion onto a non-adhesive substrate and drying. At this time, if necessary, pigment, pigment dispersant, glass beads, resin beads, high boiling organic solvent as a film forming aid, antifreeze agent, viscosity modifier, ultraviolet ray Absorbents, antioxidants, antibacterial agents, antifungal agents, etc. can be added. In addition, a surfactant type antistatic agent is used to prevent the deterioration of workability due to the generation of static electricity when the film is formed. It is preferable to mix an agent, an antistatic agent such as a conductive filler, and the like.

The substrate is not particularly limited, and examples thereof include substrates having a smooth surface such as a glass plate, a metal plate, and a synthetic resin sheet. The method of extending the fluororesin aqueous dispersion on the base material is not particularly limited, and examples thereof include, for example, Barco overnight, Floco night, Coilco night, Riki Tenco night, Air air. Any method such as spraying can be preferably used.

The method of drying the fluororesin aqueous dispersion spread on the base material is not particularly limited. For example, a method of evaporating volatile components such as water at room temperature after coating on the base material, or a method of preheating in advance A method of applying a fluororesin aqueous dispersion on a base material by a known method, and further drying and blowing in a heating furnace at a temperature of 30 to 200 ° C for about 5 seconds to 24 hours. it can. Further, a method in which the above operations are continuously performed in a continuous line up to coating, drying, cooling and film winding is also preferable. At this time, not only the water contained in the aqueous fluororesin dispersion but also the organic solvent having a low boiling point used as a plasticizer is dried so as to be 0.5% by weight or less in the coating film. It is preferable to set conditions. The residual organic solvent is not preferred because it causes tackiness of the film, lowers the blocking property, and lowers the handleability and the stain resistance.

The method for separating the film-like material dried on the substrate from the substrate is not particularly limited, and a usual mechanical method or the like can be appropriately selected and applied. The resin film is prepared by drying a fluororesin aqueous dispersion in which the resin is dispersed in an aqueous medium. The fluororesin aqueous dispersion has a basic structure in which a resin is dispersed in an aqueous medium. The aqueous medium is not particularly limited, and examples thereof include water obtained by adding an additive, a solvent, and the like described in detail below.

The resin dispersed in the aqueous medium is a fluorinated resin and other resins. In the present specification, the above-mentioned fluorine-containing resin and the other resins are collectively referred to as “resin”.

The resin dispersed in the aqueous medium is roughly classified into (1) a fluorine-containing resin comprising a copolymer of fluorinated olefin and a monomer copolymerizable therewith, and (2) a fluorinated resin. And a fluorine-based composite resin comprising another polymer. In this specification, the above (1) and (2) are collectively referred to as “resin”.

One of the resins according to the present invention is (1) a fluorinated resin comprising a copolymer of fluorinated olefin and a monomer copolymerizable therewith.

The above-mentioned fluorofluorin is not particularly restricted but includes, for example, vinyl fluoride (VF), vinylidene fluoride (Vd F), tetrafluoroethylene (TF E), black-mouthed trifluorethylene (CTFE), and hexane. Fluoroolefins having about 2 to 4 carbon atoms, such as fluoropropylene (HFP) and trifluoroethylene (TrFE). Examples of the monomer copolymerizable with the above-mentioned fluoroolefin include, for example, olefins such as ethylene, propylene, and isobutylene; ethyl vinyl ether (EVE), cyclohexyl vinyl ether (CHVE), and hydroquinyl butyl vinyl ether. (HBVE), vinyl ethers such as butyl vinyl ether, isobutyl vinyl ether, methyl vinyl ether, and polyoxyethylene vinyl ether; polyoxyethylene aryl ether, ethylaryl ether, and hydroquinethylaryl ether. Alkenyls such as vinyl acetate, aryl alcohol and aryl ether; vinyl esters such as vinyl acetate, vinyl lactate, vinyl butyrate, vinyl bivalate, vinyl benzoate, VEOVA 9 (manufactured by Shell), VEOVA 10 (manufactured by Shell). : Itaconic anhydride, succinic anhydride, And ethylenically unsaturated carboxylic acids such as crotonic acid.

Copolymers of the above-mentioned fluent olefins and monomers copolymerizable therewith are not particularly limited, and examples thereof include CTF EZ vinyl ether copolymer, CTFEZ vinyl ester copolymer, and TFE novinyl ether copolymer. Copolymer, TFE novinyl ester copolymer, TFE ethylene copolymer, TF EZ propylene copolymer, CTF E / ethylene copolymer, CTFEZ propylene copolymer, CTF EZ ethylene novinyl ether copolymer, CTF EZ ethylene / Examples thereof include vinyl ester copolymers, and those obtained by modifying these copolymers with a small amount of copolymerizable monomers.

The above-mentioned fluorinated resin exists as fluorinated resin particles in an aqueous medium.

The fluororesin aqueous dispersion is obtained, for example, by polymerizing the resin of the above (1) in a solvent or the like, and then dispersing it in water in the presence of an emulsifier to distill off the solvent. Examples of the method include the method of performing the emulsion polymerization of the resin in an aqueous medium.However, in order to reduce the solvent and simplify the process, a method of performing the emulsion polymerization in an aqueous medium is preferable. It can be carried out by the same method as the usual emulsion polymerization, for example, in a closed container, in an aqueous medium, a surfactant, a polymerization initiator, a chain transfer agent, and in some cases, a chelating agent and a pH adjusting agent. And the presence of solvents And a monomer such as a monomer copolymerizable with fluorinated olefins at a temperature of 10 to 90 ° C. for 0.5 to 40 hours.

As the above-mentioned surfactant, anionic, nonionic or a combination of anionic and nonionic can be used, and in some cases, an amphoteric surfactant can also be used.

Examples of the anionic surfactant include higher alcohol sulfates, sodium alkyl sulfonates, sodium alkyl benzene sulfonates, sodium dialkyl succinate sulfonates, alkyl diphenyl ether sulfonates, and the like. In addition to hydrocarbon-based anionic surfactants such as sodium salts, fluorinated anionic surfactants such as fluoroalkylcarboxylates, fluoroalkylsulfonates, and fluoroalkylsulfates can be mentioned. Can be. Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene ethylene phenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene alkyl phenyl esters, sorbitan alkyl esters, Glycerin esters and derivatives thereof can be mentioned.

Examples of the amphoteric surfactant include lauryl betaine.

Further, as the surfactant, a so-called reactive emulsifier can be used, and further, such a reactive emulsifier and the above-mentioned emulsifier can be used in combination.

The polymerization initiator used in the emulsion polymerization is not particularly limited as long as it generates a radical that can be subjected to a free radical reaction in an aqueous medium at a temperature of 10 to 90 ° C., and in some cases, It is also possible to use in combination with a reducing agent. Examples of such polymerization initiators include water-soluble polymerization initiators such as persulfate and hydrogen peroxide, and reducing agents such as sodium pyrobisulfite, sodium bisulfite, sodium L-ascorbinate, and Rongalite. Can be mentioned. Examples of oil-soluble polymerization initiators include diisopropyl peroxydiene carbonate (IPP), benzoyl peroxide, dibutyl peroxide, and azobisisobutyronitrile (AIBN). it can. The amount of the polymerization initiator to be used is usually 0.05 to 2.0 parts by weight per 100 parts by weight of the radically polymerizable unsaturated monomer.

Examples of the chain transfer agent used in the emulsion polymerization include halogenated hydrocarbons such as black form and carbon tetrachloride; mercaptans such as n-dodecyl mercaptan, tert-dodecyl mercaptan, and n-octyl mercaptan. And the like. The amount of the chain transfer agent to be used is generally 0 to 5.0 parts by weight per 100 parts by weight of the radically polymerizable unsaturated monomer.

The above solvents are used within a range that does not impair workability, disaster prevention safety, environmental safety, and manufacturing safety, for example, 20% by weight or less. For example, methyl ethyl ketone, acetone, and Rifluoretane, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, propanol, butanol, ethylcellosolve, butylcellosolve, methyl carbitol, ethyl carbitol, butyl carbitol, dioxane, butyl carbitol acetate, Texanol, ethyl acetate, butyl acetate and the like can be mentioned.

The addition of such a solvent may improve the swellability of the radically polymerizable unsaturated monomer in the fluororesin particles.

Another one of the resins according to the present invention is (2) a fluorine-based composite resin composed of a resin composed of a polymer of a fluent olefin and another polymer. The above-mentioned other polymer is not particularly limited. For example, a polymer composed of a radically polymerizable unsaturated monomer is preferable. The fluorofluorin copolymer is dispersed in the form of particles in an aqueous medium, and is polymerized by so-called seed polymerization when forming a fluorine-based composite resin using the radically polymerizable unsaturated monomer. In the present specification, “seed polymerization” means a reaction of polymerizing with another monomer in an aqueous medium in which resin particles are present. Accordingly, the fluorine-based composite resin means a seed polymer after the seed polymerization, and the resin particles mean seed particles in the seed polymerization.

The polymer of the fluororefin is preferably a VdF-based polymer, for example, a VdF homopolymer, a VdFZTFE copolymer, a VdF / HFP copolymer, or a VdF-no-CTFE copolymer. Polymer, Vd F / TF EZC TF E Copolymer, V d F / TF EZ HFP copolymers and the like can be mentioned.

When the fluororefin polymer is a VdF-based polymer, the fluorine-based composite resin is referred to as a VdF-based composite resin in this specification.

The polymer constituting the seed particles is preferably a VdF copolymer, and more preferably a polymer containing 70 mol% or more of VdF. When the VdF is 70 mol% or more, the compatibility between the seed particles and the polymer comprising the radical polymerizable unsaturated monomer is improved, and the film (cast) formed by drying the emulsion is formed. When the transparency and mechanical properties of the film are improved, excellent properties due to compatibility can be obtained.

The average particle diameter of the seed particles is closely related to the average particle diameter of the fluorine-based composite resin after the seed polymerization, and the average particle diameter of the fluorine-based composite resin after the seed polymerization is 50 to 300. In order to make it nm, it is preferable to be 40 to 290 nm.

The polymer constituting the seed particles can be obtained by a usual emulsion polymerization method. For example, a fluorinated reactive emulsifier having a hydrophilic moiety is present in an amount of from 0.1 to 1.0% by weight of water, and a fluorinated emulsifier is present in an amount of from 0 to 1.0% by weight. It can be prepared by emulsion polymerization of the mixture.

In addition, 1.0% by weight or less, preferably 0.5% by weight or less, more preferably 0.2% by weight or less (the lower limit is usually 0.1% by weight) of a fluorine-based surfactant relative to water is used. Monomer containing fluorofluorin in the presence of 0.01 to 0.1% by weight, preferably 0.01 to 0.05% by weight, based on water, of nonionic non-fluorinated surfactant It can be prepared by emulsion polymerization of the mixture. The aqueous dispersion obtained by these methods can stably contain side particles having an average particle diameter of not more than 0.m at a high concentration of 30 to 50% by weight.

Examples of the fluorine-containing reactive emulsifier having the hydrophilic site, for _{example, CF 2 = CF - (CF} z C FX) n Y ( wherein, is, F or CF _a, Y is, S 0 ₃ M, CO OM (M is a hydrogen atom, amine, ammonium or alkali metal), n represents an integer.), CF ₂ CF-0 (C FX) „Y (where X, Y, and η are same _{as.), CH 2 = C F-} CF 2 one _{O (CF (CF 3) CF} 2 O) " one CF CC F 3) Y (where Υ and η are the same as described above), CF ₂ = CF-CF ₂ 0 (CF (CF ₃ ) CF ₂ ◦) _n — CF (CF ₃ ) Y (where Y And η are the same as those described above.), Etc., but from the viewpoint of solubility in water and surface activity, η is preferably in the range of 0 to 3.

More specifically, a structure of CF ^ = CF—CF ₂ —O (CF (CF ₃ ) CF _z O) _n —CF (CF ₃ ) COOOH, wherein n is 0 to 2 is used.

The polymerization temperature is from 20 to 120 ° C, preferably from 30 to 70 ° C. When the polymerization temperature is lower than 20 ° C, the stability of the resulting latex generally becomes low. When the polymerization temperature is higher than 120 ° C, the polymerization rate tends to be stalled due to chain transfer. The polymerization depends on the type of the polymer, and is usually carried out by heating under a pressure of 1.0 to 50 kgf Zcm ² (gauge pressure) for 5 to 100 hours.

Examples of the fluorine-based emulsifier used in the emulsion polymerization of the seed particles include one or a mixture of two or more compounds having a fluorine atom in the structure and having surface activity. For example, an acid represented by X (CF ₂ ) „COOH (n is an integer of 6 to 20, X represents F or a hydrogen atom) and an alkali metal salt, an ammonium salt, and an amide thereof. Acid or quaternary ammonium salt; an acid represented by Y (CH ₂ CF _z ) _rn C OOH (m is an integer of 6 to 3, Y represents F or a chlorine atom) and an alkali metal salt thereof And ammonium salts, amine salts or quaternary ammonium salts. More specifically, ammonium salts of perfluorooctanoic acid, ammonium salts of perfluorononanoic acid and the like can be mentioned. In addition, known fluorine-based surfactants can be used.

In the emulsion polymerization for obtaining the seed particles, a small amount of a nonionic non-fluorinated surfactant can be used in the presence of a fluorine-based surfactant.

, Polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxyethylene ethylene sorbitan alkyl esters, glycerin esters and derivatives thereof. it can.

More specifically, polyoxyquine ethylene alkyl ethers include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxine Examples thereof include ethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene diphenyl ether. Examples of polyoxyethylene ethylene phenyl ethers include polyoxyethylene nonyl phenyl ether, polyoxyethylene nonyl phenyl ether, and polyoxyethylene nonyl phenyl ether. And polyalkylene alkyl esters, such as polyethylene glycol monolaurate, polyethylene glycol monooleate, and polyethylene glycol monostearate. Examples of the sorbitan alkyl esters include polyoxyquine sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, and monooleic acid. Can be exemplified polyoxyethylene sorbitan, etc. Examples of the glycerol esters include mono-Mi Risuchin glyceryl Monosuteari phosphate glyceryl the Monoo rain glyceryl like.

Examples of these derivatives include polyoxyethylene ethylene alkylamine, polyoxyethylene alkyl phenyl-formaldehyde condensate, and polyoxyethylene alkyl ether phosphate. Particularly preferred are polyoxetylene alkyl ethers and polyoxetylene alkyl esters having an 11:18 value of 10 to 18, and specifically, polyoxyethylene lauryl. Ether (E〇: 5 to 20; E 0 represents the number of ethylene oxide units) and polyethylene glycol monostearate (EO: 6 to 10). The other constituents of the resin according to the present invention in the fluorine-based composite resin consisting of the resin comprising the copolymer of (2) fluorinated olefin and the other polymer include the radical polymerizable as described above. Examples of the polymer include an unsaturated monomer. The radically polymerizable unsaturated monomer is not particularly limited. For example, alkyl acrylates having 1 to 18 carbon atoms in an alkyl group, and methyl acrylates having 1 to 18 carbon atoms in an alkyl group Examples thereof include acid alkyl esters and monomers having an ethylenically unsaturated unit copolymerizable therewith.

Examples of the alkyl acrylate having 1 to 18 carbon atoms in the alkyl group include methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, and the like. I-butyl acrylate, acrylic T-butyl acid, 2-ethylhexyl acrylate, lauryl acrylate, and the like.

Examples of the alkyl methacrylate having 1 to 18 carbon atoms in the alkyl group include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, N-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethyl methacrylate, cyclohexyl methacrylate, n-hexyl methacrylate And t-butyl cyclohexyl methacrylate, stearyl methacrylate, lauryl methacrylate and the like.

For the purpose of improving solvent resistance and water resistance, polyfunctional monomers such as ethylene glycol dimethacrylate and propylene glycol dimethacrylate can be copolymerized.

Examples of the monomer having an ethylenically unsaturated unit copolymerizable with the above acrylate or methacrylate include the following (I) and the following (II).

(I) Monomers having a reactive functional group, such as acrylic acid and methacrylic acid

, Maleic acid, itaconic anhydride, succinic anhydride, crotonic acid and other ethylenically unsaturated carboxylic acids; acrylamide, methacrylamide, N-methylacrylamide, N-methylolacrylylamide, N- Amido compounds such as butoxymethylacrylamide, N-methylolmethacrylamide, N-methylmethacrylamide, N-butoxymethylmethacrylamide, and the like; hydroxystyl acrylate, hydroxysethyl methacrylate Hydroxyl-containing monomers such as hydroxypropyl acrylate and hydroxypropyl methacrylate; epoxy-containing monomers such as glycidyl acrylate and glycidyl methacrylate; art methoxin lan Silanols such as methacrylate and γ-triethoxysilane methacrylate Containing monomers; Akuro aldehyde group-containing monomers such as rain.

(II) Other vinyl compounds, for example, olefins such as ethylene, propylene and isobutylene; ethyl vinyl ether (EVE), cyclohexyl vinyl ether (CHVE), hydroxybutyl vinyl ether (HBVE), butyl vinyl Vinyl ethers such as phenyl ether, isobutyl vinyl ether, methyl vinyl ether, and polyoxyethylene vinyl ether; polyoxetylene aryl ether, ethyl aryl ether, hydroxyl ethyl ether, aryl alcohol, aryl ether, and the like. Alkenyls; vinyl esters such as vinyl acetate, vinyl lactate, vinyl butyrate, vinyl bivalinate, vinyl benzoate, VEOVA 9, VE0VA10 (manufactured by Shell); itaconic anhydride, succinic anhydride, crotone Ethylenically unsaturated carboxylic acids such as acids; aromatic vinyl compounds such as styrene, α-methylstyrene, ρ-tert-butylstyrene; acrylonitrile;

As the monomer having an ethylenic unsaturated bond copolymerizable with the acrylate or the methacrylate, a low-molecular-weight polymer containing a hydrophilic site or a compound containing a ligoma in its molecule can be used. It can also be used. The above-mentioned hydrophilic site means a site having a hydrophilic group or a site having a hydrophilic bond, and a site comprising a combination thereof. The hydrophilic group may be any of ionic, nonionic, amphoteric, and a combination thereof, but is preferably a nonionic, anionic hydrophilic group. Further, a known reactive emulsifier may be used.

Examples of the acrylate, the monomer having an ethylenically unsaturated bond copolymerizable with the methacrylate, and the reactive emulsifier include, for example, polyethylene glycol methacrylate and polypropylene glycol methacrylate. , Methoxypolyethylene glycol methacrylate, polyethylene glycol acrylate, polypropylene glycol acrylate, methoxypolyethylene glycol acrylate, polyethylene glycol acrylyl ether, methoxypolyethylene glycol acrylate , Polyethylene glycol polypropylene glycol monomethacrylate, polyethylene glycol polytetramethylene glycol monomethacrylate, polyoxyethylene alkylaryl Phenyl ether, polyoxyethylene alkylaryl phenyl ether sulfate, styrene sulfonate, arylalkyl sulfonate, polyethylene glycol methacrylate sulfate, alkylaryl sulfosuccinate, bis (polyoxy Ethylene polycyclic phenyl ether) methacrylated sulfate, polyoxyethylene alkyl phenyl ether acrylate, methyl acryloyloxypolyoxyalkylene sulfate Examples thereof include ester salts, methacryloloquine alkylene sulfate salts, polyoxyethylene vinyl ether, and polyoxyethylene vinyl ester.

In the present invention, when the radical polymerizable unsaturated monomer is subjected to seed polymerization in the presence of the fluororesin particles, first, the radical polymerizable unsaturated monomer swells into the fluororesin, An aqueous dispersion of the fluorinated copolymer in which the radical polymerizable unsaturated monomer is uniformly dissolved is obtained. Thereafter, by adding a polymerization initiator, the radically polymerizable unsaturated monomer is polymerized to form compatible solution particles with entangled molecular chains. When the radically polymerizable unsaturated monomer is polyfunctional, an interpenetrating network (IPN) can be formed. Examples of the polyfunctional radically polymerizable unsaturated monomer include monoglycol dimethacrylate and diglycol dimethacrylate.

The seed polymerization of the radically polymerizable unsaturated monomer is carried out by a known method, for example, a method in which the entire amount of the radically polymerizable unsaturated monomer is charged into the reaction system in the presence of the fluorine-containing resin particles, It is possible to carry out the reaction by charging the remaining part of the radically polymerizable unsaturated monomer and then charging the remainder continuously or dividedly, or by continuously charging the entire amount of the radically polymerizable unsaturated monomer. it can. The polymerization conditions for the seed polymerization are the same as those for ordinary emulsion polymerization.For example, a surfactant, a polymerization initiator, a chain transfer agent, and, in some cases, a chelate in an aqueous medium containing fluororesin particles. The polymerization can be carried out by adding an agent, a pH adjusting agent, a solvent, and the like, and performing a reaction at a temperature of 10 to 90 ° C. for 0.5 to 6 hours.

Examples of the anionic surfactant include higher alcohol sulfates, sodium alkyl sulfonates, sodium alkyl benzene sulfonates, sodium dialkyl cononates, sodium sulfonates, and alkyl diphenyl ethers. In addition to hydrocarbon anionic surfactants such as sodium terdisulfonic acid salt, fluoroalkyl carboxylate, fluoroalkyl sulfonate, fluoroalkyl And fluorinated anionic surfactants such as sulfonic acid ester. Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene alkyl phenyl esters, and sorbitan. Alkyl esters, glycerin esters and derivatives thereof.

Examples of the amphoteric surfactant include lauryl betaine.

Further, as the surfactant, a so-called reactive emulsifier that can be copolymerized with a radical polymerizable unsaturated monomer can be used. Further, such a reactive emulsifier and the above emulsifier can be used in combination. it can.

The amount of the surfactant to be used is usually 0.05 to 5.0 parts by weight per 10 Q parts by weight of the radically polymerizable unsaturated monomer.

The polymerization initiator used in the above-mentioned side polymerization is not particularly limited as long as it generates a radical capable of being subjected to a free radical reaction in an aqueous medium at a temperature of 20 to 90 ° C. Can be used in combination with a reducing agent. As such, water-soluble polymerization initiators are usually persulfates and hydrogen peroxide, and reducing agents are sodium pyrobisulfite, sodium hydrogen sulfite, sodium laascorbate, Rongalite, etc. Can be mentioned. Examples of the oil-soluble polymerization initiator include diisopropyl peroxydicarbonate (IPP), benzoyl peroxide, dibutyl peroxide, azobisisobutyronitrile (AIBN) and the like.

The amount of the polymerization initiator to be used is usually 0.05 to 2.0 parts by weight per 100 parts by weight of the radically polymerizable unsaturated monomer.

Examples of the chain transfer agent used in the above seed polymerization include halogenated hydrocarbons such as black form and carbon tetrachloride: mercaptans such as n-dodecylmercaptan, tert-dodecylmercaptan, and n-octylmercaptan; Evenings can be mentioned. The amount of the chain transfer agent to be used is usually (! To 5.0 parts by weight) per 100 parts by weight of the radically polymerizable unsaturated monomer. 1

15 The above solvents are used within a range that does not impair workability, disaster prevention safety, environmental safety, and manufacturing safety, for example, 20% by weight or less. For example, methyl ethyl ketone, acetone, and toluene are used. Lichlorotrifluoroethane, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, propanol, butanol, ethylcelloso noreb, butyl sesolve, methyl canolebitol, ethyl carbitol, butyl carbitol, dioxane, butyl carbitol Examples include acetate, texanol, ethyl acetate, butyl acetate and the like.

The particle diameter of the fluorine-containing resin particles of the present invention in the aqueous dispersion is preferably from 50 to 300 nm. More preferably, it is 50 to 200 nm.

If the particle size is less than 5 Onm, the viscosity of the fluororesin aqueous dispersion is remarkably increased at a concentration of 30% or more, which is a practical range, which hinders the work of coating. When the particle diameter exceeds 300 nm, the sedimentation stability of the obtained fluororesin aqueous dispersion becomes poor, and even if the resin composition has the same composition, the minimum film formation temperature of the fluororesin aqueous dispersion is lowered. In addition, the film prepared from such an aqueous dispersion of a fluorine-containing resin has insufficient leveling properties, and it is difficult to obtain a high gloss coating film.

The pressure-sensitive adhesive sheet of the present invention is provided with a pressure-sensitive adhesive layer on at least one surface of the fluorine-containing resin film.

The pressure-sensitive adhesive sheet may have a pressure-sensitive adhesive layer on only one side, or may have both sides.

The pressure-sensitive adhesive layer is formed by forming a pressure-sensitive adhesive into a layer, and can be usually provided by applying a pressure-sensitive adhesive to one or both surfaces of the fluorinated resin film. The pressure-sensitive adhesive is not particularly limited, and any pressure-sensitive adhesive such as thermoplastic, pressure-sensitive, and curable can be used. For example, rosin, modified rosin, polyterpene resin, terpene phenol resin, petroleum resin, alicyclic resin Hydrogenated petroleum resin, acrylic resin, natural rubber, styrene butadiene rubber, silicon rubber and the like are preferably used.

The method of applying the pressure-sensitive adhesive is not particularly limited, and examples thereof include a bar coater and a flow coat. P

1 6

—The method of coater, coil coater, force, temperature, air spray etc. can be selected and adopted as appropriate.

In providing the pressure-sensitive adhesive layer, in consideration of the workability of the pressure-sensitive adhesive sheet of the present invention, it is preferable to provide a release paper or the like on the surface of the pressure-sensitive adhesive layer to protect the pressure-sensitive adhesive sheet until the film is attached. The release paper is not particularly limited, and for example, coated paper impregnated with a fluorine-based or silicon-based release agent is preferably used.

As one mode of the pressure-sensitive adhesive sheet of the present invention, the pressure-sensitive adhesive sheet can be appropriately colored using a fluororesin film constituting the pressure-sensitive adhesive sheet in which a pigment is dispersed. Examples of the pigment include known pigments usually used for paints and aqueous dispersion pastes of known pigments which are commercially available as processed pigments. For example, white pigments include titanium oxide, extender pigments, clay, calcium sulfate, and the like. Coloring pigments include inorganic pigments such as carbon black and metal oxides, and inorganic pigments such as phthalocyanine. Organic pigments; and their water-dispersible pastes.

As one mode of the pressure-sensitive adhesive sheet of the present invention, a decorative pressure-sensitive adhesive sheet having a pattern formed by printing the surface can be further mentioned. The printing method is not particularly limited, and examples thereof include known printing methods such as seal printing, offset printing, and silk printing. The decorative adhesive sheet can be applied, for example, as a sheet for interior decoration of a house by utilizing the excellent texture as an interior sheet.

One of the most remarkable application methods of the adhesive sheet of the present invention is a marking film. Marking films are widely used as outdoor signs, outdoor signs, indoor signs, emergency signs, traffic signs, and the like. The marking film using the pressure-sensitive adhesive sheet of the present invention is excellent in weather resistance and stain removal properties, and has workability for forming a thin film, and therefore has extremely good use characteristics.

The use form of the adhesive sheet of the present invention is not limited to the above-mentioned marking film. Other forms of use of the pressure-sensitive adhesive sheet of the present invention include, for example, a food packaging film, a pharmaceutical packaging film, an agricultural vinyl house film, a roof waterproofing film, a sales promotion paper sticker, a seal, an outdoor sign sticker, Coating film for signboards, etc. Other examples include metal materials, metal products, surface protection films for storage, protection, and damage prevention, and strippable films.

Further, in addition to the above, examples of the use form of the pressure-sensitive adhesive sheet of the present invention include, for example, roughly, a reflective sheet, a surface protection sheet, an exterior sheet, an interior sheet, and the like. Examples of the above reflective sheet include road signs, road accessories, vehicles such as automobiles, railroad crossings, lower poles, fire hydrants that reflect light toward the light source when night light is applied by inserting microscopic beads into the film. Signs, signs, decorations, artificial flowers, murals, JIS

Reflective safety signs specified in Z910, mine security signs specified in JISM700, reflective sheets for clothing, helmets, etc. can be mentioned.

The surface protection sheet is used, for example, for a metal plate such as stainless steel, aluminum, and a single steel plate, a synthetic resin such as glass, special plywood, acrylic, polystyrene, polycarbonate, and polyether sulfone.

Examples of the interior sheet include an adhesive sheet for a wall and a ceiling. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples and Examples of the present invention, but the present invention is not limited thereto. Synthesis example 1

A pressure-resistant reaction vessel equipped with a stirrer having an internal capacity of 11 was charged with 500 ml of deionized water, 0.5 g of ammonium perfluorooctanoate, 0.5 g of MYS 40 (Nikko Chemicals), and 0.05 g of nitrogen. After repeated injection and deaeration and removal of dissolved air, the mixture was mixed with a mixture monomer of VdFZTFEZCTFE at a ratio of 74/14/12 mol% to 60. And pressurized to 10 kgf / cm ² . Next, 0.2 g of ammonium persulfate was charged, and Vd FZTF E / CTF E was mixed at a ratio of 74 / \ 4/12 mol% of Vd FZTF E / CTF E so that the pressure in the tank was constant at 10 kgf / cm ^2. monomer was continuously fed, after 4 0 hours and the inside of the tank normal temperature, and the end of the return reaction to normal pressure _u

This aqueous dispersion was adjusted to pH 6.5 with 5% sodium hydrogen carbonate. Got The aqueous dispersion had a solid content of 40% and an average particle size of 120 nm. The solid content was dried in a vacuum dryer at 150 ° C. for 1 hour, and the weight after drying was expressed as a percentage of the weight of the aqueous dispersion before drying. The average particle size was measured with a laser light scattering particle size measuring device (ELS-3000 manufactured by Otsuka Electronics Co., Ltd.). Example 1

In a 200 ml four-necked flask equipped with a stirring blade, a cooling tube, and a thermometer, 100 g of the aqueous fluororesin dispersion obtained in Synthesis Example 1 was charged, and the reactive emulsifier eleminol was added thereto. 1.5 g of JS 2 (manufactured by Sanyo Chemical Industries, Ltd.) was added. After humidification in a water bath with stirring, when the tank temperature reached 80 ° C, 17.0 g of methyl methacrylate (MMA) and RMA 450 M of methoxypolyethylene glycol methacrylate (Japan) Then, an emulsion prepared by emulsifying 7 g of the mixture with 10 g of a 0.5% by weight aqueous solution of JS2 was added dropwise over 1 hour. Immediately thereafter, 1 ml of a 2% by weight aqueous solution of ammonium persulfate was added to start the reaction. Three hours after the start of the reaction, the temperature in the bath was raised to 85 ° C, kept for one hour, cooled, adjusted to pH 7 with aqueous ammonia, and then filtered through a 300-mesh wire gauze to turn pale white. Was obtained. The solid content concentration was 46%, and the average particle size was 160 nm.

The aqueous dispersion was dried, and the obtained resin was dissolved in THF. The intrinsic viscosity was measured at 30 ° C., but the obtained resin was insoluble in THF. This aqueous dispersion was poured into a 10-cm petri dish so that the thickness of the dried film became 200 μm, and dried at 50 ° C. for 2 hours. The mechanical properties of the obtained film were measured for elastic modulus and elongation at break in accordance with JISK6301. The resulting film had an elastic modulus of 110 kg / mm ^{2 at 20} and an elongation of 260%.

Separately, the aqueous dispersion obtained above was discharged into a drying oven at 120 ° C. by a spray drying method to obtain a dry powder. After washing the powder with methanol and drying, it was dissolved in dimethylformamide (DMF) to a concentration of 10% by weight, but it became a DMF solvent dispersion in which a part of the insoluble fraction remained. This dispersion was spread on a propylene plate, and the solvent was dried at room temperature for 24 hours. Then, the solvent was further dried at 80 ° C. for 24 hours. The thickness of the obtained film is 23 m, The DMF content was less than 0.1% by weight based on the film, as confirmed by gas chromatography after extraction with methanol. When the mechanical properties of this film were measured, the modulus of elasticity of the obtained film was 21 kg / mm ^{2 at 20} and the elongation was 205%. Example 2

10.0 parts by weight of water, 5.30 parts by weight of SN 507 (manufactured by San Nopco) as a dispersant, FS 0 13 B (manufactured by Dow Corning) 0.3 parts by weight of ethylene Glycol 4.0 parts by weight, 28% ammonia water 0.1 part by weight, titanium oxide Thailand CR 97 (manufactured by Ishihara Sangyo Co., Ltd.) 70.0 parts by weight are dispersed in a sand mill, and pigment A stock was prepared. Next, 0.65 parts by weight of 28% aqueous ammonia was added to 75.6 parts by weight of the aqueous fluororesin dispersion prepared in Example 1, and then 24.1 parts by weight of the pigment paste and getyl adipate were added. 5. 1 part by weight, FS 0] 3 B (manufactured by Dow Corning Co., Ltd.) as an antifoaming agent 0.1 part by weight, を 10% aqueous solution of Adekinol UH 4 20 The mixture was added in parts by weight and stirred at 400 rpm for 1 hour to obtain a white paint. In the same manner as in Example 1, the composition was spread on a glass plate to obtain a color film. Table 1 shows the mechanical properties of this film. The measurement items and test methods were as follows. Gloss: The obtained composition was spread on a glass plate using an applicator to a coating thickness of 20 mm, dried at room temperature for one week, and then a gloss meter (manufactured by Suga Test Instruments Co., Ltd.) The gloss was measured using.

Stain removal: The obtained white film is adhered on an aluminum plate with double-sided adhesive tape, sprayed with carbon dispersed in water, dried in a dryer at 40 ° C for 2 hours, and then run under running water. The surface was washed with a brush, and the discoloration due to the carbon remaining after drying was measured for color difference with Minolta DP-300, and represented by ΔΕ.

Flex resistance test: The obtained white film was subjected to a flex resistance test specified in JIS K540 in a constant temperature room at 5 ° C. Judgment was made based on how many mm in diameter of the mandrel did not crack the film. The results are shown in Table 1. A smaller value indicates that the film can follow a smaller curvature surface when attaching the film.

Weathering test: The obtained white film is subjected to 100,000 in an accelerated weathering tester (SUV). After standing for a while, the gloss retention (%) before and after that was measured. Example 3

In a 200 ml stainless steel autoclave with a stirrer, 20 g of hexyl vinyl ether (CHVE) having the composition shown in Table 1, macromonomer having a hydrophilic portion (PKA5003, manufactured by NOF Corporation) 4.5 g, ethyl vinyl ester (EVE) 11.4 g, ion-exchanged water 66.1 g, ammonium perfluorooctanoate (emulsifier) 0.35 g, potassium carbonate (Κ _ΰ C) _{〇:.,) 0. 3 5 g} , sodium hydrogensulfite (N a HS) 0. 0 2 g, persulfate Anmoniumu (initiator) 0 g of 0 8 g, cooled in an ice nitrogen gas 3.5 It was pressurized degassing so that the k gZc m ^2. This pressurized degassing was repeated twice, then degassed to 10 mmHg to remove dissolved oxygen, and then charged with 38.0 g of trifluoroethylene (CTF E), 30 ° C The reaction was carried out for 12 hours to obtain the aqueous dispersion of Synthesis Example 5. The obtained aqueous dispersion had a solid content of 48% and an average particle size of 180 nm. The obtained resin was insoluble in THF.

A white film was prepared in the same manner as in Example 2, and the physical properties of the white film were measured. The results are shown in Table 1. Example 4

In a 200-ml four-necked flask equipped with a stirring blade, a cooling pipe, and a thermometer, 100 g of the aqueous fluorinated resin dispersion obtained in Synthesis Example 1 was charged, and reacted with this. Emulsifier Eleminol JS2 (manufactured by Sanyo Chemical Industries) 1.5 g was added. The mixture was heated in a water bath with stirring, and when the tank temperature reached 80 ° C, 32.0 g of methyl methacrylate (MMA), RMA 450 M of methoxypolyethylene glycol methacrylate ( Emulsion prepared by emulsifying 1.7 g of the mixture with 10 g of a 0.5% by weight aqueous solution of JS2 was added dropwise over 1 hour. Immediately thereafter, 1 ml of a 2% by weight aqueous solution of aluminum persulfate was added to start the reaction. Three hours after the start of the reaction, the temperature in the bath was raised to 85 ° C, kept for 1 hour, cooled, adjusted to pH 7 with aqueous ammonia, and filtered through a 300-mesh wire gauze to turn pale. To obtain an aqueous dispersion of a fluorine-containing resin. Solid The form concentration was 5% and the average particle size was 157 nm. The obtained resin was insoluble in THF.

The characteristics of the film were measured in the same manner as in Example 2, and the results shown in Table 1 were obtained. Example 5

100 g of the fluororesin aqueous dispersion obtained in Synthesis Example 1 was charged into a four-neck flask having a capacity of 20 Om1 equipped with a stirring blade, a cooling pipe, and a thermometer, and a reactive emulsifier was added thereto. 1.5 g of Elminol JS2 (manufactured by Sanyo Chemical Industries) was added. The mixture was heated in a water bath with stirring. When the temperature of the tank reached 80 ° C, 50.0 g of methyl methacrylate (MMA), 0.25 g of lauryl mercaptan, and methoxypolyethylene glycol methacrylate were used. An emulsion prepared by emulsifying 1.7 g of a mixture of 1.7 g of a mixture of RMA450M (manufactured by Nippon Emulsifier) with 10 g of a 0.5% by weight aqueous solution of JS2 was added dropwise over 1 hour. Immediately, 1 ml of a 2% by weight aqueous solution of ammonium persulfate was added to start the reaction. Three hours after the start of the reaction, the temperature in the bath was raised to 85 ° C, kept for 1 hour, cooled, adjusted to pH 7 with ammonia water, and filtered through a 300 mesh wire mesh. An aqueous dispersion of a blue-white fluororesin was obtained. The solid concentration was 5%, and the average particle size was 157 nm. The intrinsic viscosity of the obtained resin measured at 30 ° C. in THF was 2.3 d 1 / g.

The characteristics of the film were measured in the same manner as in Example 2, and the results shown in Table 1 were obtained. Comparative Example 1

A blue-white aqueous dispersion of a fluorine-containing resin was obtained in the same manner as in Example 3 except that the amount of n-laurylmercaptan was changed to 0.5 g. The solid concentration was 45%, and the average particle size was 158 nm. The intrinsic viscosity of the obtained resin in THF at 30 ° C. was 1.8 d 1.

The characteristics of the film were measured in the same manner as in Example 2, and the results shown in Table 1 were obtained. Comparative Example 2

Mixing 8.5 g of MMA, 8.5 g of butyl acrylate instead of 17 g of MMA W

A blue-white aqueous dispersion of a fluorinated resin was obtained in the same manner as in Example 1 except that 22 monomer was used. The solids concentration was 46% and the average particle size was 163 nm. The obtained resin was insoluble in THF.

The characteristics of the film were measured in the same manner as in Example 2, and the results shown in Table 1 were obtained. Example 6

Based on 10 Og of the aqueous resin dispersion obtained in Example 1, 4.6 g of getyl adipate as a film-forming aid and Adekinol UH420 as a thickener (manufactured by Asahi Denka Kogyo KK) ) Was spread on a 50 x 50 cm glass plate with a 4 mi 1 applicator, and placed in a dryer at 50 ° C for 2 hours. Dried. Next, an acrylic emulsion type adhesive VinyBlan 740 (manufactured by Nissin Kagaku) as an adhesive was spread on a fluororesin film prepared on an applicator having a size of 4 m m1. After drying in a dryer at 50 C for 2 hours, release paper was laminated on the acrylic adhesive to prepare a fluororesin film laminate.

The obtained fluorine-containing resin film laminate was affixed to an indoor wall surface. After that, graffiti was painted on the surface with oil-based magic ink (red, blue, black) and left for 24 hours. After that, when wiped with ethanol, the magic ink was completely removed. The gloss of the film surface did not change.

W

2 3 Table 1

Example 7 9

A colored film was obtained in the same manner as in Example 3, except that 8 parts by weight of a commercially available pigment paste was used instead of the white pigment paste. Table 2 shows the pigment pastes used and the results.

In Table 2, “Ε-13” means A-F color Ε-13 (organic red) (Dainichi Seika)

Replacement form (Rule 26) "E-1" means AF color E-1 (organic blue) (Dainichi Seika) and "E-30" means AF color E-30 (inorganic yellow) (Dainichi Seika). , Respectively. Table 2

Example 10

The white film obtained in Example 2 was cut into a rectangular shape having a length of 5 cm and a width of 7.5 cm, and the center portion was cut out in a circular shape having a diameter of 4 cm, and the white film obtained in Example 7 was obtained. The red film was cut into a circle having a diameter of 4 cm and fitted into the hollowed-out circle of the white film to prepare a marking film representing the Japanese flag. On this backside, apply ViniBlan 740 (manufactured by Nissin Chemical Co., Ltd.) using a 4 mil applicator, dry at room temperature for 24 hours, paste on an aluminum plate, and perform SUV weather resistance test. Was done.

The gloss retention of the surface after 1000 hours was 90% or more in any color portion.

Difference paper (Rule 26) Example 1 1

The film obtained in Example 6 was cut to the size of A4 before attaching the adhesive, and the surface of this film was printed with the mark of Daikin Industries Co., Ltd. using a bubble jet printer (BJC600J manufactured by Canon Inc.). did. After drying at 50 ° C. for 2 hours, the clear coating composition was spread on a printed surface overnight at 4 mi 1 apriquet and dried in a dryer at 50 ° C. for 2 hours. Thereafter, an adhesive was applied to the back surface, and a fluorine-containing resin film laminate was prepared in the same manner as in Example 6.

The applicability of the ink was good, and there was no bleeding due to the clear paint at the time of preparing the fluorine-containing resin film laminate, and a film excellent in decorativeness was obtained. Industrial applicability

Since the fluorinated resin film of the present invention has the above-mentioned constitution, it does not use an organic solvent in the production stage, is excellent in weather resistance and stain removal properties, and has workability for forming a thin film. In addition, surface printing is possible. Further, the pressure-sensitive adhesive sheet using the fluorine-containing resin film of the present invention is excellent in weather resistance, stain removal properties and workability, and is extremely suitable for use as a marking film or the like.

Claims

The scope of the claims

1 - A fluororesin film created by cast method, the elastic modulus, 5 0 kg Zm m is ² or more, elongation, fluorine-containing resin film厶, characterized in that it is 50% or more .

2. The fluororesin finolem according to claim i, which is obtained by spreading an aqueous dispersion of a fluororesin obtained by dispersing a resin in an aqueous medium on a non-adhesive substrate and drying.

3. The resin according to claim 2, wherein the resin is a VdF-based composite resin obtained by seed-polymerizing a radically polymerizable unsaturated monomer in an aqueous medium in the presence of VdF-based resin particles. Fluorine-containing resin film.

4. The fluorine-containing resin film according to claim 1, 2 or 3, wherein the fluorine-containing resin aqueous dispersion is solvent-insoluble.

5. An adhesive sheet, characterized in that an adhesive eyebrow is provided on at least one surface of the fluorine-containing resin film according to any one of claims 1, 2, 3 and 4.

6. The pressure-sensitive adhesive sheet according to claim 5, wherein the fluororesin film is formed by dispersing a pigment.

7. The decorative pressure-sensitive adhesive sheet according to claim 5, further comprising a pattern printed on the surface.

8. A marking film using the pressure-sensitive adhesive sheet according to claim 5.